410
M. Kordian et al. · Nucleoside Analogues from Push-Pull Functionalized Branched-Chain Pyranosides
◦
at 22 C. After completing of the reaction (monitored by itored ◦by TLC) compound 10 precipitated during cooling
TLC) methanol was added, the solvent was evaporated in to 22 C. The product was filtered and recrystallized from
vacuo, and the residue was purified by column chromatog- ethanol. Yield 170 mg (78%), yellow needles. – m. p. 148 –
◦
raphy (ethyl acetate) to yield compound 7. Yield 0.142 g 152 C. – [α]2D2 = +196.9 (c = 1.0, CHCl3). – Rf = 0.1
(27%), Yellow solid; m. p. 227 ◦C. – Rf = 0.2 (ethyl acetate).
(toluene/ethyl acetate 1 : 2). – 1H NMR (250 MHz, CDCl3):
– 1H NMR (250 MHz, CDCl3): δ = 7.49 – 7.47 (m, 2H, Ph), δ = 7.61 (s, 1H, 1’-H), 7.52 – 7.50 (m, 2H, Ph), 7.34 – 7.29
7.35 – 7.32 (m, 3H, Ph), 5.64 (s, 1H, CHPh), 4.68 (br d, 1H, (m, 3H. Ph), 5.56 (s, 1H, 1-H), 5.60 (s, 1H, CHPh), 4.32
3J1,2ax = 4.2 Hz, 1-H), 4.57 (s, 1H, 2’-H), 4.40 – 4.34 (m, (dd, 1H, 2J6ax,6eq = 10.1 Hz, 3J5,6eq = 5.1 Hz, 6eq-H), 4.24
3
3
3
(dt, 1H, J4,5
=
3J5,6ax = 10.1 Hz, J5,6eq = 5.0 Hz, 5-H),
2H, 5-H, 6eq-H), 4.25 (d, 1H, J4,5 = 9.0 Hz, 4-H), 3.73
3
2
(m, 1H, 6ax-H), 3.34 (s, 3H, MeO), 3.04 (s, 6H, Me2N),
2.96 (s, 6H, Me2N), 2.85 (dd, 1H, J2ax,2eq = 14.4 Hz,
4.02 (d, 1H, J4,5 = 10.1 Hz, 4-H), 3.77 (t, 1H, J6ax,6eq
=
2
3J5,6ax = 10.1, 6ax-H), 3.38 (s, 3H, MeO), 3.11 (s, 6H,
Me2N). – 13C NMR (62.9 MHz, CDCl3): δ = 187.5 (C-3),
151.9 (C-1’), 137.2, 129.0, 128.1, 126.6 (Ph), 102.5 (CHPh),
102.2 (C-2), 97.9 (C-1), 79.2 (C-4), 69.3 (C-6), 61.6 (C-5),
53.3 (MeO), 44.0 (br, NMe2). – MS (EI): m/z(%) = 319
(28) [M+]. – C17H21NO5 (319.14): calcd. C 63.94, H 6.63,
N 4.39; found C 62.81, H 6.52, N 4.16.
3J1,2eq = 0.6 Hz, 2eq-H), 1.64 (dd, 1H, 2J2ax,2eq = 14.4 Hz,
3J1,2ax = 4.6 Hz, 2ax-H), 0.16 (s, 9H, Me3Si). – 13C NMR
(62.9 MHz, CDCl3): δ = 170.2, 169.2 (C-1’, C-3’), 137.1,
129.0, 128.2, 126.2 (Ph), 120.8 (2 CN), 102.1 (CHPh), 98.0
(C-1), 88.4 (C-2’), 80.0 (C-4), 76.5 (C-4’), 69.7 (C-6), 58.4
(C-5), 55.1 (MeO), 48.1 (C-3), 40.3 (C-2), 41.8 (Me2N), 40.4
(Me2N), 2.3 (Me3Si). – MS (EI): m/z(%) = 526 (69) [M+].
– C27H38N4O5Si (385.417): calcd. C 61.57, H 7.27, N 10.64;
found C 61.48, H 7.30, N 10.14.
(4S,5aR,8R,9aS)-2,5a,6,9a-Tetrahydro-4-methoxy-2-methyl-
8-phenyl-4H-[1,3]dioxino[4’,5’:5,6]pyrano[4,3-c]pyrazole
(11a)
Spiro{2,5-dihydro-3-dimethylamino-furan-2,8’-4’,4’a,6’,7’,
8’,8’a-hexahydro-6’-methoxy-2’-phenyl-pyrano[3,2-d]-
[1.3]dioxine}-5-ylidenemalononitrile (9)
To a solution of compound 10 (0.096 g, 0.3 mmol)
in methanol (5 ml) was added methylhydrazine (0.014 g,
◦
0.3 mmol). The mixture was stirred for 5 h at 22 C. Af-
ter completion of the reaction the solvent was removed in
vacuo and the residue purified by column chromatography
(toluene/ethyl acetate 1 : 1) to obtain 11a as yellow syrup.
Yield 0.039 g (43%). – [α]2D2 = +34.8 (c = 1.0, CHCl3). –
Rf = 0.4 (toluene/ethyl acetate 1 : 1). – 1H NMR (250 MHz,
CDCl3): δ = 7.55 – 7.52 (m, 2H, Ph), 7.35 – 7.30 (m, 3H,
Ph), 7.23 (s, 1H, 3-H), 5.74 (s, 1H, 8-H), 5.55 (s, 1H, 4-H),
Compound 7 (0.052 g, 0.1 mmol) was dissolved in abs.
dimethylformamide (3 ml). After the addition of potassium
fluoride (0.0083 g, 0.14 mmol) the mixture was stirred
for 24 h at 90 ◦C. Removing of the solvent in vacuo yielded
the row material which was purified by column chromatog-
raphy (ethyl acetate). Yield 0.023 mg (78%), yellow syrup.
– [α]2D2 = −31.3 (c 0.9, CHCl3). – Rf = 0.5 (ethyl ac-
etate). – 1H NMR (250 MHz, CDCl3): d = 7.35 (br, 5H,
4.76 (d, 1H, 3J5a,9a = 9.2 Hz, 9a-H), 4.38 (dd, 1H, 2J6ax,6eq
10.2 Hz, 3J5a,6eq = 4.6 Hz, 6eq-H), 4.13 (ddd, 1H, 3J5a,6ax
=
=
Ph), 5.63 (s, 1H, 2’-H), 5.33 (s, 1H, 4-H), 4.86 (br d, 1H,
3
10.4, 3J5a,9a = 9.2 Hz, 3J5a,6eq = 4.6 Hz, 5a-H), 3.96 (t, 1H,
ꢀ
ꢀ
J6 ,7 = 4.6 Hz, 6’-H), 4.38 – 4.19 (m, 3H, 4’eq-H, 4’a-H,
8’a-H), 3.82 (t, 1H, 2J4 ax,4 eq = 3J4 ax,4 a = 10.0 Hz, 4’ax-H),
3
2J6ax,6eq = 10.2, J5a,6ax = 10.4 Hz, 6ax-H), 3.86 (s, 3H,
ꢀ
ꢀ
ꢀ
ꢀ
MeN), 3.50 (s, 3H, MeO). – 13C NMR (62.9 MHz, CDCl3):
δ = 146.3 (C-9b), 137.3, 129.2, 128.2, 126.8 (Ph), 127.9
(C-3), 115.9 (C-3a), 102.5 (C-8), 96.0 (C-4), 75.1 (C-9a),
69.5 (C-6), 64.6 (C-5a), 55.6 (MeO), 39.2 (Me). – MS (EI):
m/z(%) = 302 (0.4) [M+]. – C16H18N2O4 (302.33): calcd.
C 63.56, H 6.00, N 9.27; found C 63.43, H 5.97, N 9.13.
3.38 (s, 3H, MeO), 3.17 (s, 3H), 3.05 (s, 3H) (Me2N), 2.83
2
3
ꢀ
ꢀ
ꢀ
ꢀ
(dd, 1H, J7 ax,7 eq = 15.2 Hz, J6 ,7 = 4.6 Hz), 2.03 (d,
1H, J7 ax,7 eq = 15.2 Hz) (7’ax-H, 7’eq-H). – 13C NMR
(62.9 MHz, CDCl3): d = 172.4, 170.5 (C-3, C-5), 136.9,
129.0, 128.1, 126.0 (Ph), 117.7, 117.3 (2 CN), 101.6 (C-2’),
97.0 (C-6’), 91.8 (C-8’), 86.5 (C-4), 76.5 (C-8’a), 69.0
(C-4’), 60.0 (C-4’a), 55.4 (MeO), 38.9, 37.3 (Me2N), 37.4
(C-7’). – MS (EI): m/z(%) = 409 (100) [M+] – HRMS
C22H23N3O5 (409.44): calcd. 409.16377; found 409.16279.
2
ꢀ
ꢀ
(2R,4aR,6S,10bS)-4,4a,6,10b-Tetrahydro-6-methoxy-9-
methyl-2-phenyl[1,3]dioxino[4’,5’:5,6]pyrano[4,3-d]-
pyrimidine (12a)
Methyl (E)-4,6-O-benzylidene-2-deoxy-2-dimethylamino-
methylene-a-D-erythro-hexopyranosid-3-ulose (10)
A
suspension of potassium carbonate (0.260 g,
1.88 mmol), 18-crown-6 (0.450 g, 1.70 mmol) and
To a solution of 1 (0.264 g, 1.0 mmol) in abs. toluene acetamidinium chloride (0.060 g, 0.6 mmol) i◦n abs. N,N-di-
(10 ml) was added N,N-dimethylformamide dimethylac- methylformamide (3 ml) was stirred at −15 C for 20 min.
etal (2.5 ml, 18.9 mmol). The resulting mixture was heated Compound 10 (0.1 g, 0.3 mmol) was added to the solu-
◦
for 12 h at 100 C. After completion of the reaction (mon- tion. The reaction mixture was stirred for another 17 h
- 10.1515/znb-2006-0406
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